Water-soluble disazo dyes containing reactive groups



3,169,125 WATER-SOLUBLE DISAZO EYES CONTAEQING REACTIVE GROUPS Hans llscher, Basel, and Carl Ryifel, Dornach, Solothurn, Switzerland, assignors to Sandoz Ltd. (A/K/A Sandoz AG), Basel, Switzerland No Drawing. Filed Get. 26, 1961, Ser. No. 147,724

Claims priority, application Switzerland, Oct. 28, 1960,

12,086/60 6 Claims. (Cl. 260-181) A This invention relates to water-soluble disazo dyes which contain reactive groups and have the formula wherein The process for the production of these reactive disazo dyes consists in reacting a water-soluble disazo dye of the formula with a functional derivative of a halogenated, saturated aliphatic acid or of a halogenated or unhalogenated, unsaturated aliphatic acid, the constituents A, B and C being so chosen that the final dye possesses the number of water solubilizing groups necessary to render it soluble in water.

' A second process consists in coupling the diazo compound of an amine of the formula with a coupling component coupling in a position adjacent to a hydroxy or amino group.

The aminoazo dye of Formula II used as starting product is obtained by coupling e.g. the tetrazo compound of 1 mol of a substituted or unsubstituted 4,4-diamino- 1,1'-diphenyl according to the invention with 1 mol of a coupling component according to the invention and 1 mol of an aminobenzene which-couples in paraposition to the amino group and may be further substituted.

Examples of suitable coupling components of the naphthalene series on which the radical A is based are hydroxynaphthalene-mono-, or -dior -trisulfonic acids such as l-hydroxynaphthalene, 4- or -5-sulfonic acid, 2-hydroxynaphthalene-4-, -6-, -7- or -8- sulfonic acid, 1-hydroxynaphthalene-3,6-, -4,6-, -4,7- or -4,8- disulfonic (III) acid, 2-hydroXynaphthalene-3,6- and -6,8-disulfonic acid, l-hydroxyand 2-hydroxynaphthalene-3,6,8-trisulfonic acid or their mixtures, Z-hydroxynaphthalene, the components coupling in acid solution: 2-amino-8-hydroxynaphthalene-6-sulfonic acid, Z-amino-S-hydroxynaphthaL ene-3,6-disulfonic acid, 2 (2,4',6-trimethyl)-phenylamino-S-hydroxynaphthalene-6-sulfonic acid, Z-aminonaphthalene-6- or -7-sulfonic acid and their N-methyl derivatives; further acylamino-hydroxynaphthalenemonoand -disulfonic acids, e.g. Z-acetylamino-S-hydroxynaphthalene-7-sulfonic acid, l-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-N-carbomethoxyaminoor 2 N-carbethoxyamino-S-hydroxynaphthalene-1,7-disulfonic acid and 1,8-dihydroxynaphthalene-3,6-disulfonic acid.

Other suitable coupling components are e.g. l-hydroxy- 4-methyl-benzene, l-(2,5'-dichloro)-phenyl-3-methyl-5- pyrazolone-4'-sulfonic acid, 1-phenyl-3-methyl-5-pyrazolone, 1 (2'-chloro-6'-methyl)-phenyl-3-methyl-5-pyrazolone, 1 phenyl 5 pyraZolone-3-carboxylic acid, acetoacetylarnino-benzene, 1-acetoacetylarnino-2,S-dimethoxybenzene, 1-pheny1-3-1nethyl-5-pyrazolone-2,4- or -2,5'-disulfonic acid or -2'-, -3'- or -4-monosulfonic acid.

Important aminobenzenes which contain the radical C are: aminobenzene, l-amino-Z- or -3-methylbenzene, 1- amino- 3 acetylaminobenzene, 1-amino-2,5-dimethoxybenzene, 1-amino-5-methyl-2-methoxybenzene, l-amino- 3-propionylor -butyrylamino-benzene, 1,3-diaminobenzene, 1-amino-2,S-dimethylbenzene, 1-amino-2,3-tetramethylenebenzene.

Examples of diamino compounds containing the radical B are e.g.

4,4'-diamino-2,2'-dimethyl-l,l'-diphenyl, 4,4-diamino-1,1'-diphenyl, 4,4-diamino 2,2'-dimethyl-l,1'-diphenyl-5-sulfonic acid, 4,4-diamino-2,2'-di1nethyl-1,l-diphenyl-6-sulfonic acid, 4,4'-diamino-l,l'-diphenyl-2,2-disulfonic acid, 4,4'-diamino-l,1-diphenyl-3,3'-disulfonic acid, 4,4-diamino-1,1'-diphenyl-2,2',5,5-tetrasulfonic acid, 4,4'-diamino-3,3'-diethyl-l,1'-diphenyl-6,6-disulfonic acid, 4,4'-diamino-3,3-dimethoXy-l,1'-diphenyl-6,6-disulfonic acid, 4,4-diamino-l,1'-diphenyl-3,3-dicarboxylic acid, 4,4'-diamino-3,3-dimethoxy-1,1-diphenyl, 4,4'-diarnino-3 ,3'-dimethyll l -diphenyl, 4,4'-diamino-3,3'-diethyl-1,l'-diphenyl, 4,4-diamino-1,l'-diphenyl-6,6-sulfone-3,3'-disulfonic acid.

The substituent D is preferably the radical of one of the following acids: chloroacetic, bromoacetic, ,G-chloroand p-bromopropionic, propiolic, acrylic, methacrylic, a-chloro-, {i-chloro-, cc-bIOIIlO- and ,B-brornoacrylic acid, 04,13- and ,Bfi-dichloroor -dibromoacrylic, trichloroor tribromoacrylic, crotonic, w, 18-, 'ybromoor -chloro crotonic, 04,}3-di0hl010CI0t0BiC, monochloroand monobromomaleic, dichloroand dibromomaleic, monochloroand monobromofuramic, dichloroand dibromofumaric acid.

The introduction of the acid radicals is most easily effected by using the corresponding acid halides, or in some cases the acid anhydrides. It is preferable to Work in an aqueous medium, if necessary in presence of an 3 organic solvent, e.g. acetone, at low temperatures, e.g. 0-20 C., and in presence of an acid binding agent such as sodium carbonate, sodium hydroxide, calcium carbonate, calcium hydroxide, sodium acetate or pyridine, which may also act as a catalyst, at a weakly acid, neutral or Weakly alkaline reaction, e.g. in the pH range 4 to 9. For acylation, the carboxylic acid chlorides are employed as such or in solution in two to five times their amount of benzene, chlorobenzene, methylbenzene, dimethylbenzone or acetone, and added dropwise to the aqueous, well buffered solution of the compound containing the amino group, at a temperature of e.g. 25 C. Acylation with the anhydrides can be carried out in a similar way.

On completion of condensation or coupling the solution or suspension may be neutralized and the final reactive dye is then salted out with sodium or potassium chloride or precipitated with acid, filtered with suction, washed and dried.

The reactive dyes conforming to the invention are suitable, depending upon their constitution, for the dyeing, padding and printing of fibers of animal origin, e.g. wool and silk; synthetic polyamide fibers, e.g. nylon; leather; cellulosic fibers, e.g. cotton, linen; fibers of regenerated cellulose, e.g. viscose filament yarn, viscose staple fiber, cuprammonium rayon; and mixtures and/ or other articles of these fibers. The optimum conditions of application vary with the type of fiber and the dyes used. Animal fibers and synthetic polyamide fibers are dyed, printed or fixed preferably in an acid, neutral or weakly alkaline medium, e.g. in presence of acetic acid, formic acid, sulfuric acid, ammonium sulfate, sodium metaphosphate etc. They can also be applied from an acetic acid to neutral medium in presence of levelling agents, e.g. polyoxyethylated fatty amines or mixtures of these and alkylpolyglycol ethers, and the bath adjusted to a neutral or weakly alkaline reaction on completion of dyeing by the addition of small amounts of an agent of alkaline reaction, e.g. ammonia, sodium bicarbonate, sodium carbonate etc., or compounds which react alkaline on heating, e.g. hexamethylene tetrarnine or urea. The goods are then well rinsed and if necessary acidified with a little acetic acid.

The dyeing, padding, printing or fixation of the dyes on cellulosic fibers is carried out advantageously in alkaline medium, e.g. in presence of sodium carbonate, sodium bicarbonate, sodium hydroxide solution, potassium hydroxide solution, sodium metasilicate, sodium borate, trisodium phosphate, ammonia etc. To avoid reduction effects during dyeing, padding or printing it is often of advantage to add a mild oxidizing agent, e.g. sodium l-nitrobenzene- 3-sulfonate. As a rule fixation of the dyestuffs on cellulosic fibers is also effected with heating. A number of the dyes, depending on the reactivity of the reactive group, can be fixed at low temperatures, e.g. 20-40 C.

The dyeings and prints on cellulosic fibers possess outstanding wet fastness properties due to the formation of a stable chemical linkage between the dye molecule and the cellulose molecule. Often the total amount of applied dye does not take part in the reaction with the fiber and the unreacted dye must then be removed from the fiber by suitable treatment such as washing and/or soaping, if necessary at higher temperatures, for which purpose synthetic detergents, e.g. alkylarylsulfonates, sodium lauryl sulfate, sodium lauryl polyglycol ether sulfate, monoand dialkylphenolpolyglycol ethers can be used. The dyeings on Wool possess excellent fastness to light, perspiration, washing, sea water, milling and dry cleaning, and in most cases good level dyeing properties.

The dyeings and prints on cotton are fast to light, perspiration, Water, sea water, alkali, washing, rubbing and dry cleaning.

In the following examples the parts and percentages are by Weight and the temperatures in degrees centigrade.

EXAMPLE 1 172 parts of 4,4-diamino-1,1-diphenyl-2,2-disulfonic acid are dissolved in 50 parts of Water with the addition of about 13.6 parts of 30% sodium hydroxide solution. After the addition of 6.9 parts of sodium nitritethe solution is run at 0-15 into a solution of 27 parts of 30% hydrochloric acid in 200 parts of water. To the tetrazo compound is added a solution of 12.3 parts of l-hydroxynaphthalene-4-sulfonic acid in 70 parts of Water. After the addition of parts of finely crushed ice, a solution of 14.8 parts of crystallized sodium acetate in 15 parts of water is added dropwise in the course of 3 hours. The coupling mass is stirred over-night at 0 and next morning adjusted to a weakly alkaline reaction with sodium carbonate. After stirring for some time the suspension is adjusted to pH 5 with dilute acetic acid, and 4.8 parts of l-amino-3-methylbenzene are added. After stirring for about 10 hours sodium hydroxide solution is added to give a weakly alkaline reaction and the solution treated with a mixture of 3 parts of blood charcoal and 3 parts of infusorial earth. After filtration the aminodisazo dye is precipitated by the addition of 30% hydrochloric acid and filtered off.

The filter residue is dissolved in 1000 parts of water at 60 and the pH of the solution adjusted to 5-7. After cooling to 05 at least 6.4 parts of fl-chloropropionyl chloride are dropped in and the mass stirred for 4 hours at this temperature. By dropwise addition of dilute sodium carbonate solution the pH value is maintained between 5 and 7. On completion of acylation the dye is precipitated with sodium chloride, suction filtered, the press cake washed with sodium chloride solution and dried. The ground dye is a red powder which dissolves in water to give red solutions.

A mercerized cotton fabric is printed with a paste of the following composition:

30 parts of the dye of this example, 100 parts of urea, 385 parts of water, 450 parts of 4% sodium alginate thickening,

10 parts of sodium 1-nitrobenzene-3-sulfonate, 25 parts of sodium carbonate 1000 parts The print is dried and fixed by steaming for 10 minutes. It is then washed in cold and warm water, soaped at the boil it necessary, rinsed again in hot and cold Water, and finally dried. A brilliant scarlet print with outstanding fastness to water treatments and good light fastness is obtained.

When in place of 4.8 parts of 1-amino-3-methyl-benzone, the equivalent amount of the following aminobenzenes: aminobenzene, l-amino-2-methylbenzene, 1- amino-3-acetylamino-, -3-propionylaminoor -3-butyrylaminobenzene, 1-amino-2.5-dimethylor 2.5 dimethoxybenzene, 1-amino-2-methoxy 5 methylbenzene, 1.3 diarninobenzene or l-arnino-2.3-tetramethylenebenzene is used, and the procedure of this example is followed in all other particulars, a scarlet dye with very similar properties is obtained.

EXAMPLE 2 76.8 parts of the disazo dye obtained by coupling 1 mol of 4-diazo-4'-acetylamino-2,2-dimethyl-1,1-diphenyl 5- sulfonic acid with 1 mol of 1-hydroxynaphthalene-4,6-disulfonic acid, splitting off the acetyl group, diazotizing and coupling with 1 mol of 1-acetylamino-3-aminobenzone, are dissolved in 2500 parts of Water. This solution is cooled to 0-5 and acylated by the gradual addition of 11.3 parts of chloroacetyl chloride with stirring. At the same time sodium bicarbonate is strewn in to maintain the pH of the solution between 5 and '7. After the addition of the chloroacetyl chloride stirring is continued for 1-2 hours at the same temperature. If the reaction is not yet completed some more chloroacetyl chloride is added. As soon as no further free amino groups are indicated the mass is neutralized with sodium carbonate solution, and the new dye salted out with sodium chloride, isolated and dried at low temperature. A red powder is obtained which dissolves in water with a clear red coloration. It is dyed on wool from an acetic acid bath in which a wetting agent can be included if necessary, and gives a brilliant scarlet dyeing of excellent levelness, very good light fastness and excellent wet fastness.

2 parts of the above-described dye are dissolved in 4000 parts of water at room temperature and the solution heated to 40, with the subsequent addition of 2 parts of acetic acid and 3 parts of a mixture of a polyoxyethylated fatty amine and an alkyl polyglycolether. 100 parts of a wool fabric are entered in this bath which is then brought to the boil in 15-20 minutes and held at the boil for 45-60 minutes. At 85-90 about 5 parts of 5% ammonia or 3 parts of hexamethylene tetramine are added and treatment continued for 20 minutes at 90. The dyed wool is then thoroughly rinsed with a little acetic acid 6 EXAMPLE 3 69.8 parts of the disazo dye obtained by tetrazotizing 1 mol of 4,4'-diamino-1,1-diphenyl-2,2'-disulfonic acid and subsequent coupling with 1 mol of l-hydroxynaphthalene-4-sulfonic acid and 1 mol of 1,3-diaminobenzene, are gradually added in portions to a mixture at 20-40 of 80 parts of chloroacetic acid, 50 parts of sulfuric acid monohydrate and 20 parts of 60% oleum so that the temperature does not rise to above 40. At the same time 80 parts of 65% oleum are run in slowly. The mass is subsequently stirred for 12-15 hours at room temperature. The next morning no further free amino groups are indicated. The reaction mass is run into ice and .the precipitated dye filtered ofi, stirred into 2000 parts of cold water and neutralized with 20% sodium carbonate solution. It is then salted out, and the sodium salt of the dye formed filtered oil and dried at low temperature with vacuum.

A red powder is obtained which dissolves in water e lot of therrgismg Wate? P s fi 3 1 12 20 with a scarlet coloration and .dyes wool and polyamide dyemgfast to was W 2 l Ion an 1111 mg an wlt fibers, if necessary with the addition of a wetting agent, good 11gb? fastness 1S f m 1 m in level shades very fast to light and wet treatments. when Place of 1 Parts 0 c Proacety C onde The following table-contains further valuable dyes of P of 5' P chlonde 9 Parts 9 the Formula I, which can be obtained according to the acrylic acid chloride or 13.2 parts of monochloromaleic 2o particulars f Examples 1 to 3 and are characterized by acid anhydride are used, dyes with very similar propthe symbols A, B, C and D and by the shade of their erties are obtained. dyeings on wool.

Table B=Radical Bound in 4,4 and Coupling Component for the Shade of A: Derlved from Introduction of the Radical O D= Dyeing No. on Wool (I) (II) (III) (IV) (V) l-hydroxy-ISIfi-disulfO-Z-nflPhthYL -d etl y1- ,1-diphenyl-5- Aminobenzene Chloracetyl Orange.

W sulfonic acid. 2-hydroxy-G-sulio-l-naphthyl .do l-amino-2,5-dimethylbenzene fl-Chloropropionyl Do. l-hydroxy-i,6-d1sulIo-2-naphtuy.. ,3-dlmethoxy- ,1 diphcnyl. l-amino-3-aeetylaminobenzene. u-Ch1oracrylyl. Violet. 1-hydlifi:1 1y-13,6,8tfiSl1lf0-2 2-2-d1me hy1l,1-iphenyl 1-amino-2,5-dimethylbenzene Acrylyl Red.

nap y. z-hydilotllily-l3flfl'tlisulf0-1- 1-1-d1pheny1 Lamina-2,S-dimethoxybenzene. a,B-dichloracrylyl Do.

p Y- z-hydroxy-l-naphthyl 1, -c bphenyl; 2,5,2,5-tetra- Aminobenzene 'y-Ohlorocrotonylu Scarlet.

Sll omc a0 1-hydroxy-4,fI-disulfo-2-naphtl1yl- 2,2-dimethyl-1,l-diphenyl-6- 1-amino-2-methoxy-5-methyl- Triehloracrylyl. Do.

sulfonle acid. benzene. l-hydroxy-4-sulfo-2'naphthyl 1,1-diphenyl-3,3-disulionie acid--. l-aamino-2,3-tetramethylene- Ohloracetyl Orange.

enzene. 12 do 3,3-diethy1- ,1-diphenyl-6,6- 1-amino-3-methylbenzene .do Scarlet.

disulfonic acid. 13 1-hydroxy-5-su1io-2-naphthyl 1,1-diphenyl-3-suli'onic acid l-aamino-li-propionylamino- Bromacetyl Orange.

enzene. 14-- 1-hydroxy-8,6-disulio-2-naphthyl 2,2-dimet l(11yl-1,1-diphe11yl5-sull-amino-3-methylbenzene Propiolyl Do.

ome aei 15 l-hydroxy-et-sulio-Z-naphthyl 3,3 dgethyl-lfi.diphenyl-6,6-di- 1-amino-2,S-dimethylbenzene Ohloracetyl Scarlet.

su 0111c ae1 do do 7 H l-amino-Z-mcthylbenzene do Do. -hydroxy-3,6-disulio-l-naphthyl 2-2f-d imet l(i1yl-1,1-diphenyl-5-suldo fi-Bromopropionyl Orange.

onic ael l-hydgtgy-f-sulio-G-chloro-Z- d0 -L l-arnino-fz,5-dimethylbenzene Methaerylyl Scarlet.

D Y- 19 1-hydroxy-4,8-disulfo-2-naphthyl- 1,l-dphenyl3,3-dicarboxylic Aminobenzene afi-Dibi-Iom- Red.

aci acryly. 20 l-hydroxy-B,5-disulio-8-amino-2- 2,2-dimethyl-1,1-diphenyl-6-sul- 1-amino-3-methoxy-benzene Ghloracetyl Violet.

naphthyl. ionic acid. 7 21 1-lt1gdi oxy-3,6,8-trisulfo-2-naph- 3,3-dimethyl-1,l-dipheny1 Lamino-Z,fi-dimethylbenzene Crotonyl Red.

. Y 22 Lhydroxy-3,8-d1su1Io-2-naphthyl 2,2f'-d 1metl(11yl-1,1'-d1pheny1-5 sull-amino-3-butyry1-aminobenzene. fl-Clilorzfpro- Orange.

0111c aci piony 23 2-]gd1roxy-3fi,G-trisulfo-l-naph- 3,3-diethyl-l,1-diphenyl l-amino-Z,S-dimethylbenzene a-Bromacrylyl Do.

. y 24 2-hydroxy-7-sulfo-l-naphthy1 1-1-dipheny1-3-suli0uic acid do fifi-Dichlor- Do,

V V acry yl. 25 2-acetylamino-5-hydroxy-7-sulfo-6- 1,1-diphenyl-2,2-Su1ione-5,5-dido -Bromoerotonyl Violet.

naphthyl. sulfonic acid. 26 2-hydroxy-8-sulio-l-napbthyl 3,3-dimethoxy-1,1-dipl1eny1-6,6- Aminobenzene 01,}3-Di0h1010- Do.

7 disulionie acid. crotonyl. 27 l-hydroxy-i-sulfo-6-ehloro-2-napl1- 1,1-diphenyl-2,2-disulfonic acid... l-arnino-2,5-dimethylbenzene fl-Chloro-B-car- Scarlet thyl. v boxy-aerylyl. 28 2-1)euzoy1amm0-5-hydr0xy-7-Su1f0- do -do a-Oliloro-fi-ear- Violet. G-naphthyl. boxy-aerylyl. 29 2-amino-6-suli0-1-naphthyl 2,2'-dimethyl-l,1-dipheny1-5-sul- 1-amino-3-methylbcnzene.. a,B-Dichlor0/3- Red.

suliouic acid. carboxy-aerylyl. 30 l-hydroxy-B-benzoylamiuo-3,6-did0 1-amin0-2,5-dimethy1benzene a-BIOHIO'B-CDI- Violet.

sulfo-Z-naphthyl. boxy-acrylyl. 31 2-1nethylamino-fi-sulio-l-naphthyl do do B-Bromo-B-car- Red.

. boxy-acrylyl. 32 2-amino-7-sulfo-l-naphthyl d0 1-amino-3-methylbenzene a-OhlorocrotonyL. Violet. 33 l-hydroxy-3,S-disulfo-2-naphthyl 1,1-(1lfiph enyl -(;2,2-sulfone-5 5-di- '1-amino-3-pr0pi0nyl-amin0hen- Tribromacrylyl..- Orange su onie aei zene. 34 1,sfiihydroxy-3,6-disulfo-2-naph- 2,?-dimet1(1iy1-1,l-dip11eny1-5-su1- Aminobenzene Bromacetyl Violet.

t y onie aei l 35 2-carbethoxyamino-5-l1ydroxy-7- 1,1-diphenyl-2,2-disulionic acid-.- l-amino-Z,S-dimethylbenzene fl-BromoerotonyL Do.

sulfo-fi-naphthyl.

. 3,169,125 A 9 1G Formulae of representative dyes of the foregoing examples are as follows:

EXAMPLE 1 ()H slosH N=N@N=N@NHO -cH,0H2-c1 SOGH CH3 SO3H (last paragraph) ()H S|O3H ([Jm l 80 K CH3 SOsH EXAMPLE 2 J11 #0311 (3H3 H03 8- CH3 NH-CO-CHa EXAMPLE 3 ?H SIOSH 803K NH-CO-CHzCl I I S0311 EXAMPLE 12 OH cm, SiO H SOaH EXAMPLE 15 |3H 02115 S0311 (3H3 1 $0311 C2115 CH3 Having thus disclosed-the invention, what we claim is: C is a 1,4-phenylene radical selected from the group 1. Disazo dyestufiof the formula consisting of o SO H OH H Y t 0 H S 3 :113 whereln OH CHa the group consisting of Z-hydroxynaphthalene, l-hydroxynaphthalene monosulfonic acid, l-hydroxynaphthalene-disulfonic acid, l-hydroxynaphthaleneall trisulfonic acid, 2-hydroxy-naphthalene-monosulfonic acid, 2 hydroxynaphthalene-disulfonic acid, 2-hydroxynaphthalene-trisulfonic acid, OH being in a position adjacent to the 2120 group, 1;

l l A is the radical of a coupling component selected from I Ha NH-C O-lower alkyl 3,169,125 11 i2 and C is a 1,4-phenylene radical selected from the group D is an acyl radical selected from the group consisting consisting of of halogenoacetyl, fi-halogenopropionyl, propiolyl, CH3

methacrylyl, acrylyl, a-halogenoacrylyl, 8-halogenoacrylyl, ac halogeno-crotonyl, halogeno-crotonyl, 5 C a-halogeno-B-carboxy-acrylyl, fl-halogeno-B-carboxyacrylyl and a,fi-dihalogeno-fl-carboxy-acrylyl, halo- CH3 gen having an atomic weight between 35 and 81.

2. Disazo dyestufi of the formula (3H3 so rr CH; 10 on A N N N N O NE D CH3 lH-CO-lower alkyl OH; and wherein O is the radical of a coupling component selected from and the group consisting of Z-hydroxynaphthalene, l-hy- D is an acyl radical selected from the group consisting droxynaphthalene monosulfonic acid, l-hydroxyof halogenoacetyl, fi-halogenopropionyl, propiolyl, naphthalene-disulfonic acid, l-hydroxynaphthalenemethacrylyl, acrylyl, a-halogenoacrylyl, fi-halogenotrisulfonic acid, 2-hydroxy-naphthalene-monosulfonic acrylyl, a-halogeno-crotonyl, fi-halogeno-crotonyl, uacid, 2 hydroxynaphthalene-disulfonic acid, 2-hyhalogeno-fl-carboxy-acrylyl, fi-halogeno-fi-carboxydroxynaphthalene-trisulfonic acid, OH being in a posiacrylyl and a.,B-dihalogeno-fi-carboxy-acrylyl, halotion adjacent to the azo group, gen having an atomic weight between and 81.

3. The disazo dye of the formula 11 S|O3H l 1 s03]: 0H3

soaH

4. The disazo dye of the formula OH S OQH (3H3 N=N-N=N.- -NH-C o-cm-cm-m S0313 CH3 5. The disazo dye of the formula 01-1 s oaH (3H3 H03s- CH3 NH-OO-OH3 6. The disazo dye of the formula on S|O3H (EH N=N- N=N NHCOCH C H03s soan CH3 No references cited.

CHARLES B. PARKER, Primary Examiner, 

1. DISAZO DYESTUFF OF THE FORMULA
 2. DISAZO DYESTUFF OF THE FORMULA 